JP2001022083A - Composition for underlayer film of resist and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for an underlayer film of a resist excellent in adhesion to the resist and resistance to a developing solution and less liable to reduce film thickness in the oxygen ashing of the resist. SOLUTION: The composition contains (A) a hydrolyzate and/or a condensation product of a compound of the formula R1aSi(OR2)4-a [where R1 is H, F or a monovalent organic group, R2 is a monovalent organic group and (a) is 0-2] or the formula R3b(R4O)3-bSi-(R7)d-Si(OR5)3-cR6c [where R3-R6 are each a monovalent organic group, (b) and (c) are each 0-2, R7 is 0 or -(CH2)n-, (d) is 0 or 1 and (n) is 1-6], (B) a solvent of the formula R8O(CHCH3CH2O)cR9 [where R8 and R9 are each H, 1-4C alkyl or CH3CO- and (e) is 1-2] and (C) a compound which generates an acid when irradiated with light and/or heated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a resist underlayer film, and more particularly to a resist solution having excellent reproducibility and resolution, excellent adhesion to a resist, and a developing solution used after exposing the resist. Excellent resistance,
The present invention also relates to a composition for a resist underlayer film, which causes less film loss during oxygen ashing of the resist.

[0002]

2. Description of the Related Art Fine patterning of organic materials and inorganic materials is performed by lithography technology, resist development process, and pattern transfer after resist development for pattern formation of semiconductor devices and the like. However, as the degree of integration of semiconductor elements and the like increases, it becomes difficult to accurately transfer a pattern to a resist in an exposure step, and the processing dimensions may be deviated in a substrate processing step. Therefore, an anti-reflection film for reducing the effect of standing waves, which is a cause of an irregular processing size, is indispensable in a fine processing process. As such an anti-reflection film, there is a lower anti-reflection film formed between the resist and the substrate.

On the other hand, when a substrate such as a silicon oxide film or an interlayer insulating film is processed, a resist pattern is used as a mask. It becomes difficult to process the oxide film without giving. Therefore, a process is first performed in which the resist pattern is first transferred to a lower layer film for processing an oxide film / interlayer insulating film, and then the oxide film / interlayer insulating film is dry-etched using the film as a mask. The lower film for processing an oxide film or an interlayer insulating film refers to a film which also functions as a lower antireflection film or a film formed below the antireflection film. In this process, since the etching rate of the resist and the lower layer film for processing the oxide film / interlayer insulating film are close to each other, the distance between the resist and the lower layer film is
It is necessary to form a mask capable of processing the lower layer film. In other words, on the oxide film, the lower film for processing the oxide film and the interlayer insulating film is formed.
A multilayer film of a mask and a resist for processing the lower layer film is formed.

[0004] The characteristics required for a mask for processing an underlayer film include the ability to form a resist pattern without tailing, excellent adhesion to a resist, and sufficient masking properties when processing an underlayer film for processing an oxide film. However, there is no material that satisfies all the requirements.

According to the present invention, in order to solve the above-mentioned problems, the resist is not peeled off by improving the reproducibility of a pattern by providing the resist in a lower layer, and is resistant to alkali and oxygen ashing during removal of the resist. Another object of the present invention is to provide a resist underlayer composition having excellent storage stability.

The present invention, (A) (A-1 ) R 1 a Si (OR 2) that compounds represented by the following general formula _{(1) 4-a ····· (} 1) (R 1 is A hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) represented by the following general formula (2). the compound ^{_{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ····· (2) (R 3, R 4, R 5 And R ⁶ may be the same or different and each represents a monovalent organic group, b and c may be the same or different and each represent a number of 0 to 2, and R ⁷ represents an oxygen atom or- (CH ₂ ) _n- , d is 0 or 1
And n represents a number of 1 to 6. )) (At least one compound selected from the group consisting of
(B) a solvent represented by the following general formula (3): R ⁸ O (CHCH ₃ CH ₂ O) _e R ⁹ (3) (R ⁸ and R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—
Represents a valent organic group, and e represents an integer of 1 to 2. And (C) a compound for generating an acid upon irradiation with ultraviolet light and / or heating (hereinafter also referred to as “acid generator”), and a method for producing a resist underlayer film, and a method for producing the same. is there.

(A) Component In the general formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Further, in the general formula (1), R ¹ is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like, preferably having 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched, Further, a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), as the aryl group,
Examples include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane, tri- sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane,
Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, etc .; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltrimethylsilane -N-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane,
Methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-s
ec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri- sec-butoxysilane, vinyl tri-tert
-Butoxysilane, vinyltriphenoxysilane, n-
Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane,
n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-
sec-butoxysilane, n-propyltri-tert
-Butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri- n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri- n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-te
rt-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-
n-propoxysilane, sec-butyl-tri-iso
-Propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxy Silane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-
n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrisilane -Iso-
Propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, etc .; dimethyldimethoxysilane , Dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec
-Butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n -Butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-
tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso- Propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl-di- Phenoxysilane, di-i
so-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-
Propoxysilane, di-iso-propyl-di-iso
-Propoxysilane, di-iso-propyl-di-n-
Butoxysilane, di-iso-propyl-di-sec-
Butoxysilane, di-iso-propyl-di-tert
-Butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n
-Butyldiethoxysilane, di-n-butyl-di-n-
Propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di- tert-butoxysilane, di-n
-Butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane,
Di-sec-butyl-di-iso-propoxysilane,
Di-sec-butyl-di-n-butoxysilane, di-s
ec-butyl-di-sec-butoxysilane, di-se
c-butyl-di-tert-butoxysilane, di-se
c-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxy Silane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxy Silane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-s
ec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, and the like. (A
-1) Of the components, preferably, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n- Propoxysilane,
Methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n- Butyltriethoxysilane, i-butyltrimethoxysilane,
i-butyltriethoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyl Dimethoxysilane, diphenyldiethoxysilane, trimethylmonomethoxysilane,
Examples thereof include trimethylmonoethoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triphenylmonomethoxysilane, and triphenylmonoethoxysilane. These may be used alone or in combination of two or more.

In the above formula (2), examples of the monovalent organic group include the same organic groups as those in the above formula (1). In the general formula (2), examples of the compound in which R ⁷ is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane,
1,1,1,3,3-pentamethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaethoxy-3-
Methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3
-Pentaethoxy-3-phenyldisiloxane, 1,
1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3 -Diphenyldisiloxane, 1,1,3,3-
Tetraethoxy-1,3-diphenyldisiloxane,
1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triethoxy-1,3,3-
Trimethyldisiloxane, 1,1,3-trimethoxy-
1,3,3-triphenyldisiloxane, 1,1,3-
Triethoxy-1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3
-Tetramethyldisiloxane, 1,3-dimethoxy-
1,1,3,3-tetraphenyldisiloxane, 1,3
-Diethoxy-1,1,3,3-tetraphenyldisiloxane and the like. Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-
1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3
Dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3
Preferred examples include 3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane. Compounds in which d is 0 in the general formula (2) include hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,1,2,2-pentamethoxy-2
-Methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2
-Pentaethoxy-2-phenyldisilane, 1,1,
2,2-tetramethoxy-1,2-dimethyldisilane,
1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-
1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,
1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2
-Tetramethyldisilane, 1,2-diethoxy-1,
1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2
-Diethoxy-1,1,2,2-tetraphenyldisilane or the like, wherein R ⁷ in the general formula (2) is-(CH ₂ ) _n-
Examples of compounds of the formula are bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (hexaphenoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, and bis (dimethoxyphenyl) (Silyl) methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, bis (ethoxydiphenylsilyl) methane, bis (hexamethoxysilyl) ) Ethane, bis (hexaethoxysilyl) ethane, bis (hexaphenoxysilyl) ethane, bis (dimethoxymethylsilyl) ethane, bis (diethoxymethylsilyl) ethane, bis (dimethoxyphenylsilyl) ethane, Bis (diethoxyphenylsilyl) ethane, bis (methoxydimethylsilyl) ethane, bis (ethoxydimethylsilyl) ethane, bis (methoxydiphenylsilyl) ethane, bis (ethoxydiphenylsilyl) ethane, 1,3-bis (hexamethoxysilyl) ) Propane, 1,3-bis (hexaethoxysilyl) propane, 1,3-bis (hexaphenoxysilyl) propane, 1,3-bis (dimethoxymethylsilyl) propane, 1,3-bis (diethoxymethylsilyl) Propane, 1,3-bis (dimethoxyphenylsilyl) propane, 1,3-bis (diethoxyphenylsilyl) propane, 1,3-bis (methoxydimethylsilyl) propane, 1,3-bis (ethoxydimethylsilyl) propane , 1,3-bis (methoxydiphenylsilyl) Propane, 1,3-bis (ethoxy-butyldiphenylsilyl) propane and the like. Among them, hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2
2-tetraethoxy-1,2-dimethyldisilane, 1,
1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2
-Tetramethyldisilane, 1,2-diethoxy-1,
1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2
-Diethoxy-1,1,2,2-tetraphenyldisilane, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis ( Preferred examples include dimethoxyphenylsilyl) methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, and bis (ethoxydiphenylsilyl) methane. It can be mentioned as. In the present invention, two or more compounds (1) can be used.

In the present invention, it is particularly preferable that the component (A) is as follows or is particularly preferable since the adhesion to the resist is better. A hydrolyzate of a compound represented by the following general formula (5) and / or a condensate thereof: Si (OR ² ) ₄ (5) (R ² represents a monovalent organic group; (The same as formula (1).) A hydrolyzate of a compound represented by the general formula (5) and a silane compound composed of a compound represented by the following general formula (6) and / or a condensate thereof: R ¹ _n Si (oR ²⁾ _{4 over n} (6) (R ¹ and R ² may be the same or different, each represents a monovalent organic group, specific examples are the same as the general formula (1), In the above case, the compound represented by the general formula (6) (in terms of a completely hydrolyzed condensate) is converted into a compound represented by the general formula (5) (in terms of a completely hydrolyzed condensate). ) 0.5 to 100 parts by weight
30 parts by weight, more preferably the content of the component (C) is 0.1%.
5 to 25 parts by weight. In the present invention, the completely hydrolyzed condensate refers to —OR ² and —O in compound (1).
A group represented by R ³ is completely hydrolyzed by 100% hydrolysis to form an OH group.

When the compound (1) is hydrolyzed or partially condensed, a group 1 represented by R ¹ O—, R ⁴ O— or R ⁵ O—
It is preferable to use 0.25 to 3 mol of water per mol, and it is particularly preferable to add 0.3 to 2.5 mol of water. When the amount of water to be added is in the range of 0.3 to 2.5 mol, there is no possibility that the uniformity of the coating film is reduced, and the storage stability of the composition for a resist underlayer film is reduced. This is because there is little fear. Specifically, water is intermittently or continuously added to an organic solvent in which the compound (1) is dissolved. At this time, the catalyst may be added in advance to the organic solvent, or may be dissolved or dispersed in water at the time of adding water. The reaction temperature at this time is usually 0 to 100.
° C, preferably 15 to 80 ° C. By adding the component (B) to the solution subjected to these treatments, the composition for a resist underlayer film of the present invention can be obtained. When two or more compounds (1) are used, (a) two or more compounds (1) may be mixed and then hydrolyzed or condensed,
(B) Two or more types of compounds (1) may be separately hydrolyzed and condensed and then used as a mixture.
Is preferred.

Component (B) In the present invention, the compound represented by the general formula (3)
Examples of the alkyl group of (1) to (4) include a methyl group, an ethyl group, and n-
Examples thereof include a propyl group, an i-propyl group, and a butyl group. As the compound represented by the general formula (3), 1
-Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-i-propoxy-2-propanol,
1-n-propoxy-2-propanol, 1-i-butoxy-2-propanol, 1-n-butoxy-2-propanol, 1-tert-butoxy-2-propanol, etc., and particularly 1-methoxy-2 -Propanol, 1-ethoxy-2-propanol, 1-i-propoxy-2-propanol, 1-n-propoxy-2-propanol are preferred. These can be used alone or in combination of two or more. The compound represented by the general formula (3) is the component (A) (complete hydrolyzed condensate) 100
To parts by weight to parts by weight, preferably to
Parts by weight are included.

(C) Component In the present invention, examples of the acid generator include a latent thermal acid generator and a latent photoacid generator. Latent thermal acid generator used in the present invention, usually 50 ~ 450 ℃,
Preferably, it is a compound that generates an acid by heating to 200 to 350 ° C, and an onium salt such as a sulfonium salt, a benzothiazolium salt, an ammonium salt, and a phosphonium salt is used.

Specific examples of the above sulfonium salt include 4
-Acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-
4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-
Alkylsulfonium salts such as 4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate; benzyl -4-Hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl -2-methyl-4-hydroxyphenylmethylsulfonium hexafluoro Nchimoneto, benzyl-3-chloro-4-hydroxyphenyl methyl sulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl methyl sulfonium hexafluorophosphate, benzoin tosylate, 2
Benzylsulfonium salts such as -nitrobenzyl tosylate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, Dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-
tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-
Dibenzylsulfonium salts such as 4-hydroxyphenylsulfonium hexafluorophosphate; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chloro Benzyl-4
-Hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-
4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4
Substituted benzylsulfonium salts such as -hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate;

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, (P-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5
Benzylbenzothiazolium salts such as -chlorobenzothiazolium hexafluoroantimonate. Furthermore, as thermal acid generators other than the above, 2, 4,
4,6-tetrabromocyclohexadienone can be exemplified.

Of these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium
Hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate Nates and the like are preferably used. These commercial products include Sun-Aid SI-L85,
I-L110, SI-L145, SI-L150,
And SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.). These compounds can be used alone or in combination of two or more.

The latent photoacid generator used in the present invention comprises:
It is a compound that generates an acid when irradiated with ultraviolet light of usually 1 to 100 mJ, preferably 10 to 50 mJ. Examples of the photoacid generator include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, and diphenyliodonium. Nonafluoro n-
Butanesulfonate, bis (4-t-butylphenyl)
Iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium naphthalene sulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4 -T-butylphenyl) iodonium nonafluoro n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl (4- Methylphenyl) sulfonium trifluoromethanesulfonate, diphenyl (4-methoxyphenyl) sulfate Trifluoromethanesulfonate, (hydroxyphenyl) benzenemethylsulfonium toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfoniumtrifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfoniumtrifluoromethanesulfonate, dimethyl (2-oxocyclohexyl) sulfoniumtrifluoromethane Sulfonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium camphorsulfonate, (4-hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfone 4-cyano 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyl-diethylsulfonium Trifluoromethanesulfonate, 4
-Nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfoniumtrifluoromethanesulfonate,
4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-ethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (1-methoxyethoxy) -1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-methoxyethoxy) -1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxycarbonyloxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbenyloxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- n-butoxycarbyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1- Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-
(2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1-
Onium salt-based photoacid generators such as (naphthyl acetomethyl) tetrahydrothiophenium trifluoromethanesulfonate; phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl- Halogen-containing compound-based photoacid generators such as bis (trichloromethyl) -s-triazine; 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2,3,4 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1,4'-tetrabenzophenone or 1,2-naphthoquinonediazide-5
Diazoketone compound-based photoacid generators such as sulfonic acid esters; sulfonic acid compound-based photoacid generators such as 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane; benzoin tosylate, pyrogallol Trinitrotrifluoromethanesulfonate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2,2,1] hept-5-ene-2,3-
Examples thereof include sulfonic acid compound-based photoacid generators such as dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate. These can be used alone or in combination of two or more. In the present invention, the amount of the component (C) used is 1 to 100 parts by weight of the component (A) (in terms of complete hydrolysis and condensate).
-30 parts by weight, more preferably 1-10 parts by weight.
When the content of the component (C) is 1 to 30 parts by weight, the amount of resist footing is small, and the undercut of the resist pattern can be further reduced.

Component (D) The composition of the present invention may contain a catalyst. Examples of the catalyst used at this time include a metal chelate compound, an organic acid, an inorganic acid, an organic base, and an inorganic base. Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, and tri-n-butoxy.・ Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (acetylacetonato) titanium, di-se
c-butoxy bis (acetylacetonate) titanium,
Di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n-propoxytris (acetylacetonato) titanium, mono-i-propoxytris (acetylacetonate) ) Titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) ) Titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate)
Titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy.
Mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-
n-propoxybis (ethylacetoacetate) titanium, di-i-propoxybis (ethylacetoacetate) titanium, di-n-butoxybis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetate) Acetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxytris (ethylacetoacetate) titanium, mono-n-propoxytris (ethylacetoacetate) titanium,
Mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris ( Ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl acetoacetate)
Titanium chelate compounds such as titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxymono (acetylacetonate) zirconium, tri-n- Propoxy mono (acetylacetonate) zirconium, tri-i-propoxy mono (acetylacetonate) zirconium, tri-n-butoxy mono (acetylacetonate) zirconium, tri-sec-butoxy mono (acetylacetonate) Zirconium, tri-t-butoxy mono (acetylacetonate) zirconium, diethoxybis (acetylacetonate) zirconium,
Di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxybis (acetylacetonato) zirconium, di-n-butoxybis (acetylacetonato) zirconium, di-sec-butoxybis ( Acetylacetonato) zirconium, di-t-butoxybis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxy・ Tris (acetylacetonate) zirconium,
Mono-n-butoxy tris (acetylacetonate)
Zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri- n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium,
Tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) Zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-
t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium, mono-n-propoxytris (ethylacetoacetate) zirconium, mono-i-propoxytris (ethylacetoacetate) zirconium Mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-
Butoxy / tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) zirconium, tris (acetylacetate) Zirconium chelate compounds such as (nate) mono (ethylacetoacetate) zirconium; aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, and gallic acid , Butyric, melitic, arachidonic, mykimic, 2-ethylhexanoic, oleic, stearic, linoleic,
Linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid,
Monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like can be mentioned. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like. As the organic base, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclookran, diazabicyclononane , Diazabicycloundecene, tetramethylammonium hydroxide and the like. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.
Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and titanium chelate compounds and organic acids are more preferable. These may be used alone or in combination of two or more.

The amount of the catalyst to be used is generally 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the component (A) (in terms of complete hydrolysis condensate).
The range is 0 parts by weight.

In the present invention, the following organic solvent may be further contained. Here, as the organic solvent, for example, n-pentane, i-pentane, n-hexane, i-pentane
Hexane, n-heptane, i-heptane, 2,2,4-
Aliphatic hydrocarbon solvents such as trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n
-Propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene,
Aromatic hydrocarbon solvents such as di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol , N-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-pentanol
Hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol -4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, s
ec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-
Trimethylcyclohexanol, benzyl alcohol,
Phenylmethylcarbinol, diacetone alcohol,
Monoalcohol solvents such as cresol; ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2, 4,2-ethylhexanediol-
Polyhydric alcohol solvents such as 1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin; acetone,
Methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i
-Butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone Ketone solvents such as acetone alcohol, acetophenone and fenchone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide,
Dioxolan, 4-methyldioxolan, dioxane,
Dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-
n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n- Butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomer Ether solvents such as toluene ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ -Butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-acetic acid
-Butyl, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, acetic acid Methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene acetate Glycol monomethyl ether, propylene glycol monoethyl ether acetate,
Propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate,
Methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate,
Ester solvents such as ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide;
Acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-
Nitrogen-containing solvents such as methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone; and the like, preferably propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Dipropylene glycol monopropyl ether, dipropylene glyco Monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol mono Butyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol diacetate,
Dipropylene glycol diacetate, propylene glycol and the like, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate are particularly preferred from the viewpoint of storage stability of the solution.
These can be used alone or in combination of two or more. Further, the content of these organic solvents is preferably less than 50% by weight of the compound represented by the general formula (3).

The resist underlayer film composition of the present invention can be obtained by subjecting compound (1) to hydrolysis, hydrolysis and / or condensation in the compound represented by formula (3). The hydrolysis and condensation of compound (1) are preferably performed in the presence of the catalyst.

In the composition of the present invention, the content of alcohol having a boiling point of 100 ° C. or less is preferably 2% by weight or less, particularly preferably 1% by weight or less from the viewpoint of uniformity of the coating film. Boiling point 100 ° C
The following alcohols hydrolyze compound (1) and / or
Or, it may occur during the condensation, and its content is 2
It is preferable to remove it by distillation or the like so as to be not more than 1% by weight, preferably not more than 1% by weight. Further, the content of water in the composition is preferably 1% by weight or less, particularly preferably 0.95% by weight or less from the viewpoint of coating film uniformity. The water used in the hydrolysis of the compound (1) may remain in some cases, and may be removed by distillation or the like so that the content becomes 1% by weight or less, preferably 0.95% by weight or less. preferable. Further, the content of sodium and iron in the composition is preferably 20 ppb or less, particularly preferably 15 ppb or less from the viewpoint of the resolution of the resist. Sodium and iron may be mixed in from the raw materials used, and it is preferable to purify the raw materials by distillation or the like.

The composition of the present invention may further contain the following components. β-diketones β-diketones include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- Nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2
6,6-tetramethyl-3,5-heptanedione, 1,
One or more kinds such as 1,1,5,5,5-hexafluoro-2,4-heptanedione. In the present invention, the content of β-diketone in the composition for a resist underlayer film is preferably 1 to 50% by weight, more preferably 3 to 30% by weight of the total solvent. If β-diketone is added in such a range, a certain storage stability can be obtained, and there is little possibility that the properties such as coating uniformity of the composition for a resist underlayer film are reduced.

Other components such as colloidal silica, colloidal alumina, an organic polymer, and a surfactant may be further added to the composition for a resist underlayer film obtained in the present invention. The colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5%.
-30 μm, preferably 10-20 μm, and the solid content concentration is about 10-40% by weight. As such colloidal silica, for example, Nissan Chemical Industries, Ltd.
Methanol silica sol and isopropanol silica sol; Oscar, etc., manufactured by Sekiyu Kasei Kogyo Co., Ltd. Nissan Chemical Industry Co., Ltd.
Alumina Sols 520, 100, and 200 manufactured by Kawaken Fine Chemical Co., Ltd .; Examples of the organic polymer include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylate compound, a polyester,
Polycarbonate, polyanhydride, aromatic vinyl compound, dendrimer, polyimide, polyamic acid, polyarylene, polyamide, polyquinoxaline,
Examples thereof include polyoxadiazole and a fluoropolymer. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a silicone surfactant, a polyalkylene oxide surfactant And fluorinated surfactants and acrylic surfactants. As a specific example of the surfactant,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether;
Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octyl phenyl ether and polyoxyethylene n-nonyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; Polyesters; tertiary amine-modified polyurethanes; polyethylene imines, etc., as well as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.) ), Megafac (Dainippon Ink and Chemicals, Inc.), Florard (Sumitomo 3M), Asahi Guard, Surflon (
Asahi Glass Co., Ltd.), Disperbyk (Big Chemie Japan Co., Ltd.), Solsperse (Zeneca Co., Ltd.)
Manufactured). These surfactants can be used alone or in combination of two or more.

The total solid content of the composition for a resist underlayer film of the present invention is usually 1 to 20% by weight, preferably 1 to 10% by weight, and is appropriately adjusted depending on the purpose of use. When the total solid content of the composition is 1 to 20% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. Further, all polyorganosiloxane components in the composition thus obtained [hydrolysis condensate of component (A)]
Is usually 500 to 120,000,
Preferably it is about 800 to 100,000.

In order to further improve the adhesion between the resist underlayer film of the present invention and the resist, the surface of the resist underlayer film may be subjected to a methylsilylation treatment. Examples of the silylation agent include allyloxytrimethylsilane, N, O-
Bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, bis (trimethylsilyl) urea, trimethylchlorosilane, N- (trimethylsilyl) acetamide, trimethylsilyl azide, trimethylsilyl cyananide, N- (trimethylsilyl) imidazole, 3-trimethylsilyl-2- Oxazolidinone, trimethylsilyl trifluoromethanesulfonate, hexamethyldisilazane, heptamethyldisilazane, hexamethyldisiloxane, N-methyl-
N-trimethylsilyl trifluoroacetamide,
(N, N-dimethylamino) trimethylsilane, nonamethyltrisilazane, 1,1,3,3-tetramethyldisilazane, trimethyliodosilane, and the like can be given. Methylsilylation of the resist underlayer film can be performed by dip coating or spin coating the above silylating agent on the resist underlayer film, or by exposing the resist underlayer film to a vapor atmosphere of the silylating agent. After that, the coating may be heated to 50 to 300 ° C.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described.
A description will be given based on examples. However, the following description generally shows an example of the embodiment of the present invention, and without any particular reason,
The description is not intended to limit the invention.

The composition for a resist underlayer film was evaluated by the following method. (Evaluation of Resist Adhesion) An antireflection film (NFC B007 manufactured by JSR) was applied on a silicon wafer by spin coating, and dried on a hot plate at 190 ° C. for 1 minute. The thickness of the obtained antireflection film was 300 nm.
Next, the resist underlayer film composition was applied by spin coating, and dried on a hot plate at 190 ° C. for 2 minutes.
At this time, the thickness of the resist underlayer film was controlled to 70 nm.
Further, a resist (M20 manufactured by JSR) is formed on the resist underlayer film.
G) was applied and dried at 135 ° C. for 90 seconds. At this time, the thickness of the resist was controlled to 700 nm. Nikon KrF excimer laser irradiation device (trade name: NSR-
2205 EX8A) and a KrF excimer laser (wavelength 248 nm) of 0.18 to 0.25 μm (0.1
The substrate was irradiated with 22 mJ through a quartz mask having a line and space pattern of every μm. Thereafter, the substrate was heated at 135 ° C. for 90 seconds. 2.38% aqueous solution of tetramethylammonium hydroxide
After developing for 0 second, the resist pattern was
And the case where the development peeling of the resist pattern did not occur was judged as “no peeling”.

(Evaluation of Resolution of Resist Pattern) On the substrate after the development, the resist pattern was observed with an SEM, and a resist pattern in which no undeveloped resist remained on the exposed portion was defined as a minimum resolution.

(Evaluation of Alkali Resistance) The resist underlayer film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 30 seconds, and the film thickness before and after the immersion was 2%.
In the case of nm or less, it was judged as “good”.

(Oxygen Ashing Resistance) A barrel type oxygen plasma ashing apparatus (PR-5 manufactured by Yamato Scientific Co., Ltd.)
01A), it was determined to be “good” if the change in film thickness before and after O ₂ treatment at 300 W for 15 seconds was 5 nm or less.

(Storage Stability of Solution) A composition for a resist underlayer film stored at 45 ° C. for one month was placed on a silicon wafer.
Using a spin coater, the number of rotations is 2,000 rpm,
The coating was performed under the condition of 0 seconds. Thereafter, using a hot plate maintained at a temperature of 190 ° C., the silicon wafer coated with the composition for a resist underlayer film was heated for 2 minutes to form a coating film on the silicon wafer. The film thickness of the coating film thus obtained is measured by an optical film thickness meter (Rudolph Te).
Spectra Race, manufactured by technologies
r200), and 50 points were measured in the coating film surface. The film thickness of the obtained film thickness was measured, and the storage stability was evaluated based on the film thickness increase rate determined by the following equation. Film thickness increase rate (%) = ((film thickness after storage) − (film thickness before storage)) ÷ (film thickness before storage) × 100 Good: film thickness change rate ≦ 10% defective: 10% <film Thickness change rate

Synthesis Example 1 In a quartz separable flask, 30.1 g of distilled tetramethoxysilane was dissolved in 154 g of distilled propylene glycol monopropyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 80 ° C. . Next, 15.7 ion-exchanged water in which 0.12 g of maleic acid was dissolved.
g was added to the solution over 1 hour. Then, at 80 ° C, 4
After reacting for an hour, the reaction solution was cooled to room temperature. 50 ℃
After removing 51 g of a solution containing methanol from the reaction solution by evaporation, 51 g of distilled propylene glycol monopropyl ether was added to obtain a reaction solution. The content of sodium in the obtained composition was 1.1 ppb, the content of iron was 1.7 ppb, the content of alcohol having a boiling point of 100 ° C. or lower was 0.6% by weight, and the content of water was 0.4% by weight. .

Synthesis Example 2 In a quartz separable flask, 30.1 g of distilled tetramethoxysilane and 0.03 g of diisopropoxytitanium bisethylacetyl acetate were dissolved in 174 g of distilled propylene glycol monomethyl ether, followed by stirring with a three-one motor. The solution temperature was stabilized at 80 ° C. Next, 15.7 g of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 80 ° C. for 4 hours, the reaction solution was cooled to room temperature. After removing 51 g of a solution containing methanol from the reaction solution at 50 ° C. by evaporation, 51 g of distilled propylene glycol monomethyl ether was added to obtain a reaction solution. The resulting composition had a sodium content of 1.2 ppb and an iron content of 1.8 ppb.
b, The content of alcohol having a boiling point of 100 ° C. or less was 0.8% by weight, and the content of water was 0.5% by weight.

Synthesis Example 3 In a quartz separable flask, 24.1 g of distilled methyltrimethoxysilane was dissolved in 165 g of distilled propylene glycol monoethyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 80 ° C. Was. Next, ion-exchanged water in which 0.12 g of maleic acid is dissolved.
5 g was added to the solution over 1 hour. Then, after reacting at 80 ° C. for 4 hours, the reaction solution was cooled to room temperature. 50
After removing 34 g of a solution containing methanol from the reaction solution by evaporating at 34 ° C., 34 g of distilled propylene glycol monoethyl ether was added to obtain a reaction solution. The sodium content in the obtained composition was 1.2 ppb, the iron content was 1.8 ppb, the alcohol content at a boiling point of 100 ° C. or lower was 0.8% by weight, and the water content was 0.5% by weight. .

Synthesis Example 4 A reaction solution was obtained in the same manner as in Synthesis Example 1 except that distilled butyl acetate was used instead of distilled propylene glycol monopropyl ether. The content of sodium in the obtained composition was 1.1 ppb, the content of iron was 1.7 ppb, the content of alcohol having a boiling point of 100 ° C. or lower was 0.7% by weight, and the content of water was 0.3% by weight. .

Example 1 To 50 g of the reaction solution obtained in Synthesis Example 1, 0.09 g of triphenylsulfonium trifluoromethanesulfonate was added as the component (B), and the mixture was sufficiently stirred. Add this solution to 0.
Filtration was carried out with a Teflon filter having a pore size of 2 μm to obtain a composition for a resist underlayer film of the present invention. Evaluation Results Adhesion of resist: no peeling Resolution of resist pattern: 0.17 μm Alkali resistance: good (film thickness change: 0.4 nm) Oxygen ashing resistance: good (film thickness change: 2.4 nm) Solution storage stability: good (film) (Thickness increase rate 4.7%)

Example 2 To 50 g of the reaction solution obtained in Synthesis Example 1, 0.09 g of triphenylsulfonium nonafluoro-n-butanesulfonate was added as the component (B), and the mixture was sufficiently stirred. This solution was filtered through a Teflon filter having a pore size of 0.2 μm to obtain a composition for a resist underlayer film of the present invention. Evaluation Results Adhesion of resist: no peeling Resolution of resist pattern: 0.18 μm Alkali resistance: good (film thickness change: 0.5 nm) Oxygen ashing resistance: good (film thickness change: 2.7 nm) Solution storage stability: good (film) (Thickness increase rate 4.5%)

Example 3 To 50 g of the reaction solution obtained in Synthesis Example 2, 0.09 g of triphenylsulfonium trifluoromethanesulfonate was added as the component (B), and the mixture was sufficiently stirred. Add this solution to 0.
Filtration was carried out with a Teflon filter having a pore size of 2 μm to obtain a composition for a resist underlayer film of the present invention. Evaluation result : Adhesion of resist: no peeling Resolution of resist pattern: 0.18 μm Alkali resistance: good (change in film thickness: 0.7 nm) Oxygen ashing resistance: good (change in film thickness: 3.0 nm) Solution storage stability: good (film) (Thickness increase rate 3.6%)

Example 4 To 45 g of the reaction solution obtained in Synthesis Example 1, 5 g of the reaction solution obtained in Synthesis Example 3 and 0.09 g of triphenylsulfonium trifluoromethanesulfonate as the component (B) were added, and the mixture was sufficiently stirred. This solution was filtered through a Teflon filter having a pore size of 0.2 μm to obtain a composition for a resist underlayer film of the present invention. Evaluation Results Adhesion of resist: no peeling Resolution of resist pattern: 0.16 μm Alkali resistance: good (thickness change: 0.3 nm) Oxygen ashing resistance: good (thickness change: 3.1 nm) Solution storage stability: good (film) (Thickness increase rate 3.4%)

Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that triphenylsulfonium trifluoromethanesulfonate was not added as the component (B). Evaluation results : Adhesion of resist: no peeling Resist pattern resolution: poor (0.25 μm resolution not possible) Alkali resistance: good (film thickness change 0.8 nm) Oxygen ashing resistance: good (film thickness change 2.9 nm) Solution storage Stability: good (film thickness increase rate 5.0%)

Comparative Example 2 Synthesis Example 4 50 g of the obtained reaction solution and 0.09 g of triphenylsulfonium trifluoromethanesulfonate as the component (B) were added and sufficiently stirred. Add this solution to 0.2
The solution was filtered through a Teflon (registered trademark) filter having a pore size of μm to obtain a composition for a resist underlayer film of the present invention. Evaluation Results Adhesion of resist: no peeling Resolution of resist pattern: 0.24 μm Alkali resistance: good (film thickness change: 1.0 nm) Oxygen ashing resistance: good (film thickness change: 3.4 nm) Solution storage stability: poor (film) (Thickness increase rate 16.3%)

[0044]

According to the present invention, the resolution of the resist pattern, the adhesion to the resist, the resist, and the like can be obtained by adding a compound capable of generating an acid upon irradiation with ultraviolet light and / or heating to the hydrolysis condensate of the alkoxysilane. It is possible to provide a composition for a resist underlayer film having excellent resistance to a developing solution used after exposure to light, excellent resistance to oxygen ashing of a resist, and excellent storage stability of a solution.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kinji Yamada 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Akio Saito 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Incorporated (72) Inventor Yoshihisa Ota 2--11-2 Tsukiji, Chuo-ku, Tokyo FSR term in JSR Corporation (reference) 2H025 AA04 AA09 AA11 AA14 AB16 BE00 CC03 CC20 DA25 DA34 DA35 DA40 FA41 5F046 NA07 PA07

Claims (9)

[Claims] (A) (A-1) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) (R ¹ is a hydrogen atom, A fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) a compound represented by the following general formula (2) _{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (oR 5) 3-c R 6 c ····· (2) (R 3, R 4, R 5 and R ⁶ May be the same or different and each represents a monovalent organic group, b and c may be the same or different and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom or — (CH ₂ ) _{Represents n-} , d is 0 or 1
And n represents a number of 1 to 6. Or (B) a solvent represented by the following general formula (3): R ⁸ O (CHCH ₃ CH ₂ O) _e , a hydrolyzate and / or a condensate of at least one compound selected from the group consisting of: R ⁹ ... (3) (R ⁸ and R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—.
Represents a valent organic group, and e represents an integer of 1 to 2. And (C) a compound for generating an acid upon irradiation with ultraviolet light and / or heating. 2. Component (A) (in terms of complete hydrolysis condensate)
The content of the component (C) is 1 to 30 with respect to 100 parts by weight.
The composition for a resist underlayer film according to claim 1, wherein the composition is in parts by weight. 3. The composition for a resist underlayer film according to claim 1, wherein the water content in the composition for a resist underlayer film is 1% by weight or less. 4. The composition for a resist underlayer film according to claim 1, wherein the boiling point of the composition for a resist underlayer film is 100.
A composition for a resist underlayer film, wherein the content of alcohol at a temperature of not more than 2 ° C is 2% by weight or less. 5. The composition for a resist underlayer film according to claim 1, wherein the content of sodium and iron in the composition for a resist underlayer film is 20 ppb or less. 6. The composition for a resist underlayer film according to claim 1, further comprising a metal chelate compound represented by the following general formula (4) and / or an acid catalyst. R ¹⁰ _f M (OR ¹¹ ) _gf (4) (R ¹⁰ is a chelating agent, M is a metal atom, and R ¹¹ is a compound having 2 to 2 carbon atoms.
5 represents an alkyl group or an aryl group having 6 to 20 carbon atoms, g represents the valence of the metal M, and f represents an integer of 1 to g. ) 7. The composition for a resist underlayer film according to claim 1, wherein the component (A) is a hydrolyzate of a compound represented by the following general formula (5) and / or a condensate thereof. object. Si (OR ² ) ₄ (5) (R ² represents a monovalent organic group.) 8. A hydrolyzate of a silane compound wherein the component (A) is a compound represented by the following general formula (5) and a compound represented by the following general formula (6) and / or a condensate thereof: The composition for a resist underlayer film according to claim 1, wherein _{^{Si (OR 2) 4 ····· (}} 5) (R 2 is a monovalent organic _{^{group.) R 1 n Si (OR}} 2) 4 _{over n ·····} (6) (R ¹ And R ² may be the same or different and each represents a monovalent organic group, and n represents an integer of 1 to 2.) 9. A hydrolytic condensate of a compound represented by the following general formula (5) and a hydrolyzed condensate of a compound represented by the following general formula (6) are mixed.
The method for producing the composition for a resist underlayer film according to the above. _{^{Si (OR 2) 4 (5}} ) (R 2 is a monovalent organic _{^{group.) R 1 n Si (OR}} 2) 4 _{over n} (6) (R ¹ and R ² be the same or different Each represents a monovalent organic group, and n represents an integer of 1 to 2.)